CN110760813B - Preparation method of carbon-encapsulated metal nanoparticles with controllable layer number - Google Patents
Preparation method of carbon-encapsulated metal nanoparticles with controllable layer number Download PDFInfo
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- CN110760813B CN110760813B CN201810831980.8A CN201810831980A CN110760813B CN 110760813 B CN110760813 B CN 110760813B CN 201810831980 A CN201810831980 A CN 201810831980A CN 110760813 B CN110760813 B CN 110760813B
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- cobalt
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- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 239000002245 particle Substances 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
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- -1 cation salts Chemical class 0.000 claims abstract description 15
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
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- 150000001768 cations Chemical class 0.000 claims description 4
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
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- 230000033228 biological regulation Effects 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
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- 239000010949 copper Substances 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
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- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229960004011 methenamine Drugs 0.000 claims description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010936 titanium Substances 0.000 claims description 2
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- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
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- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 38
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 11
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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- B82Y40/00—Manufacture or treatment of nanostructures
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开了一种层数可控的碳封装金属纳米颗粒的制备方法及其在电催化分解硫化氢制氢反应中的应用。具体地说，该方法是一种基于共沉淀的方法，将金属阳离子盐转化为层状金属氢氧化物沉积在二氧化硅球表面，经过还原气氛热处理后引入碳源，并使用氢氟酸溶液去除二氧化硅球，即得到目标产物。该方法所制备的材料中碳层石墨化程度高，层数较少且可控制，被碳封装的金属纳米颗粒为单质态或合金态，颗粒尺寸分布均一。本方法是一种制备碳封装一元、二元或多元金属纳米颗粒的普适方法，具有简单，易于操作和碳层数可控制的特点。该材料作为电催化分解硫化氢制氢电极材料展现出了优异的活性和广阔的应用前景。
The invention discloses a preparation method of carbon-encapsulated metal nanoparticles with a controllable number of layers and its application in the electrocatalytic decomposition of hydrogen sulfide to produce hydrogen. Specifically, the method is a co-precipitation-based method in which metal cation salts are converted into layered metal hydroxides and deposited on the surface of silica spheres, after heat treatment in a reducing atmosphere, a carbon source is introduced, and a hydrofluoric acid solution is used. The target product is obtained by removing the silica spheres. In the material prepared by the method, the carbon layer has a high degree of graphitization, and the number of layers is small and controllable. The metal nanoparticles encapsulated by the carbon are in a simple substance state or an alloy state, and the particle size distribution is uniform. The method is a general method for preparing carbon-encapsulated mono-, binary or multi-element metal nanoparticles, and has the characteristics of simplicity, easy operation and controllable carbon layers. The material exhibits excellent activity and broad application prospects as an electrode material for electrocatalytic decomposition of hydrogen sulfide for hydrogen production.
Description
Technical Field
The invention relates to a preparation method of carbon-encapsulated metal nanoparticles with controllable layer number and application of the carbon-encapsulated metal nanoparticles in electrocatalytic decomposition of hydrogen sulfide.
Background
Hydrogen sulfide (H)2S) is a toxic gas, largely associated with natural gas development and petroleum processing (Petrol Process petrochem.30.1 (1999)). The hydrogen sulfide can be decomposed to obtain clean energy hydrogen and chemical raw material elemental sulfur, so that an environment-friendly, low-energy-consumption and efficient technology is developed to decompose the hydrogen sulfide, the pollution of harmful gases can be eliminated, and huge economic value can be obtained. At present, the Claus process is mostly used industrially to treat hydrogen sulfide to obtain elemental sulfur, but H2Hydrogen in S is converted into water to be discharged, resulting in waste of hydrogen resources (ind. eng. chem. res.44.7706 (2005)). The electrocatalytic decomposition of hydrogen sulfide to produce hydrogen (electrocalorim. acta 243.90(2017)) has the advantages of wide application range, environmental protection, capability of recycling hydrogen resources and the like, but the development of the technology is limited by the activity of electrode materials. Noble metals such as Pt (J.Appl.electrochem.13.783(1983)) and Au (J.Appl.electrochem.27.507(1997)) are difficult to popularize and apply in a large range due to low reserves and high price; graphite materials (J.Appl.electrochem.29.521(1999)) are low in price and low in activity, and non-noble metals and oxides thereof (J.Appl.electrochem.22.927(1992)) are easy to corrode and passivate in long-time tests, so that the challenge of finding a cheap, efficient and corrosion-resistant catalytic material still exists.
Non-noble metal nanoparticles are easily oxidized in air, resulting in changes in their physicochemical properties. The carbon with higher graphitization degree is used for thoroughly encapsulating the carbon, so that agglomeration and oxidation of non-noble metal particles can be effectively prevented. And because the internal metal transfers electrons to the surface of the carbon layer, the electronic structure of the carbon surface is modulated, and the catalytic activity of the surface of the carbon layer which is originally chemically inert is excited (Angew. chem. int. Ed.52,371 (2013)). The material is widely applied to the fields of electrocatalysis of water cracking (Angew. chem. int.Ed.53,4372(2014)), oxygen reduction reaction (Angew. chem. int.Ed.53,3675(2014)), metal-air battery (ACS Nano 9,6495(2015)) and the like. At present, the synthesis of the carbon layer packaged non-noble metal nano material mainly utilizes a high-temperature pyrolysis method and a chemical vapor deposition method, wherein the number of layers of the carbon layer is still difficult to be effectively regulated and controlled, and a large number of carbon tubes are generated in the preparation process. At present, controlling the generation amount of carbon tubes, preparing relatively uniform carbon-encapsulated non-noble metals, and regulating the number of carbon layers still have certain challenges.
Disclosure of Invention
According to the invention, metal cation salts are precipitated on the surface of the silicon dioxide spheres, and a carbon source is introduced by utilizing a chemical vapor deposition method to form the carbon-encapsulated metal nanoparticle material. Specifically, the method is a coprecipitation-based method, metal cation salts are converted into layered metal hydroxides to be deposited on the surfaces of silica spheres, a carbon source is introduced after the layered metal hydroxides are subjected to reducing atmosphere heat treatment, and a hydrofluoric acid solution is used for removing the silica spheres, so that a target product is obtained. The method is a universal method for preparing the carbon-encapsulated univalent, binary or multivariate metal nanoparticles, and has the characteristics of simplicity, easy operation and controllable carbon layer number.
The invention provides a preparation method of a carbon-encapsulated metal nano-particle material, which comprises the following steps: (1) converting metal cation salt and alkaline precursor into layered metal hydroxide by a coprecipitation method, and depositing the layered metal hydroxide on the surface of the silicon dioxide nanospheres; (2) roasting in a reducing atmosphere to reduce the metal hydroxide into metal, introducing a carbon source, and depositing a carbon layer on the surface of the metal by using a chemical vapor deposition method; (3) and removing the silicon dioxide by acid etching to obtain the carbon-encapsulated metal nano-particle material.
The method realizes the regulation of the carbon layer deposited on the metal surface by regulating the time for introducing the carbon source.
The metal cation in the metal cation salt in the step (1) is at least one of magnesium, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc or ruthenium; the metal cation salt is at least one of nitrate, sulfate, chloride or acetate of the metal cation; the metal cation salt is preferably metal cobalt and metal nickel; the alkaline precursor is at least one of urea, hexamethylene tetramine, ammonium fluoride, sodium hydroxide, sodium carbonate or ammonia water; the diameter size of the silicon dioxide ball is one of 20-400 nm; the mass ratio of the metal cation salt to the silicon dioxide nanospheres is 0.1-5: 1; the molar ratio of any two of the more than two metal cation salts is 1: 20-20: 1; the coprecipitation temperature is 80-140 ℃, and the treatment is carried out for 6-24 hours.
The ratio of inert atmosphere to hydrogen in the reducing atmosphere in the step (2) is 1-5: 1; the inert gas is one of nitrogen, argon or helium.
The temperature of the programmed heating end point is 500-1000 ℃, and the temperature rising rate of the programmed heating is 0.5-20 ℃/min; the end point temperature is preferably 600-900 deg.C, and more preferably 800-900 deg.C.
The carbon source is at least one of methanol, ethanol, pyridine, pyrrole, acetonitrile, methane, ethane, ethylene, acetylene or propylene.
The flow rate of the introduced carbon source is 10-500 mL/min, and the maintaining time is 5-60 minutes.
And (4) in the step (3), hydrofluoric acid solution with the concentration of 5-20% is adopted for acid etching, and the treatment time is 4-8 hours.
The invention also provides a carbon-encapsulated metal nanoparticle material prepared by the method, wherein metal nanoparticles are independently encapsulated in a carbon layer in a metal state or an alloy state, and the particle size of the metal nanoparticles is 4-8 nm; preferably, the carbon-encapsulated metal particle material metal nanoparticles are dispersed on the in-situ generated carbon nanotubes (the generation amount of the carbon nanotubes is changed by regulating and controlling the roasting temperature); preferably, the carbon layer is 1, 2 or 3 layers (the carbon layer is controlled by controlling the introduction time of the carbon source).
In another aspect, the invention provides the carbon-encapsulated metal nano-particle material as an electrode material applied to a hydrogen production system by electrocatalytic decomposition of hydrogen sulfide.
The invention has the following advantages:
1. the prepared carbon-encapsulated metal nano-particle material has uniform particles, the metal nano-particles encapsulated by carbon are in a simple substance state or an alloy state, the graphitization degree of a carbon layer is high, and the number of carbon layers is small and controllable.
2. The metal species in the prepared carbon-encapsulated metal nanoparticles is easy to modulate, can be single-component, double-component or multi-component, has uniform particle size distribution, wide application range, easily controlled conditions, easy operation and higher product yield.
3. The encapsulated metal nanoparticles are protected by the carbon layer and cannot be corroded and oxidized under severe conditions.
4. The catalyst shows excellent catalytic performance in a hydrogen production system by electrocatalytic decomposition of hydrogen sulfide.
5. The material is expected to have potential application prospect in the fields of energy storage, catalysis, biomedicine, adsorption and the like.
Drawings
FIG. 1 is a transmission electron micrograph of carbon encapsulated metallic nickel in example 2.
FIG. 2 is a transmission electron micrograph of the carbon encapsulated metallic cobalt nickel in example 3.
FIG. 3 is a transmission electron micrograph of the carbon encapsulated metallic cobalt nickel in example 4.
FIG. 4a is a graph of the coating of cobalt nickel layered hydroxide (CoNi-LDH) on SiO in example 52Transmission Electron Microscopy (TEM) images of the surface of the sphere (70 nm); FIG. 4b is the growth of carbon-encapsulated cobalt-nickel metal nanoparticles on SiO in example 52TEM images of the surface of the sphere (70 nm); FIG. 4c shows the removal of SiO by acid etching in example 52High Resolution Transmission Electron Microscopy (HRTEM) images of carbon encapsulated cobalt nickel metal nanoparticles obtained after spheronization (70 nm).
FIG. 5a is the growth of carbon-encapsulated cobalt-nickel metal nanoparticles on SiO in example 82TEM image of the surface of a sphere (400 nm); FIG. 5b shows the removal of SiO by acid etching in example 82HRTEM of carbon encapsulated cobalt nickel metal nanoparticles obtained after spheronization (400 nm).
FIGS. 6a, b, c show the growth of carbon encapsulated cobalt nickel metal nanoparticles on SiO in examples 9, 10 and 112HRTEM of the surface of a sphere (400 nm); FIG. 6d shows the sample of example 12, i.e., the acid etch removes SiO2TEM images of carbon encapsulated cobalt nickel metal nanoparticles obtained after the spheronization.
Fig. 7 is an XRD characterization of carbon encapsulated cobalt nickel metal nanoparticles in example 3, example 4, example 5 and example 6.
FIG. 8 is a graph showing the performance of application example 1 in the electrocatalytic decomposition reaction of hydrogen sulfide.
FIG. 9 is a graph showing the performance of application example 2 in the electrocatalytic decomposition reaction of hydrogen sulfide.
Detailed Description
The whole material preparation process is described in detail by the following examples, but the scope of the claims of the present invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied for achieving the purpose.
(1) Dissolving one or more than two metal cation salts and an alkaline precursor in an aqueous solution under stirring until the solution is clear and transparent, and ultrasonically dispersing silicon dioxide spheres in the solution;
(2) placing the dispersed solution in the step (1) in a round-bottom flask, and performing reflux treatment for 6-24 hours at 80-140 ℃ under stirring;
(3) washing the suspension obtained in the step (2) by using deionized water, centrifuging, and drying the sample in vacuum;
(4) placing the dried sample in the tube furnace, carrying out temperature programming to 500-1000 ℃ under the hydrogen-argon mixed atmosphere, introducing a carbon source at the temperature, keeping the flow rate at 10-500 mL/min, and keeping the flow rate for 5-60 minutes;
(5) treating the sample obtained in the step (4) in a hydrofluoric acid solution for 4-8 hours to remove the silicon dioxide template; then washing with water and ethanol respectively, and performing suction filtration until the solution is neutral;
(6) and (5) drying the sample to obtain the carbon-encapsulated metal nanoparticle material.
In the step (2), the preferable reflux temperature is 80-120 ℃, and the preferable reflux time is 10-20 hours;
in the step (3), the preferable vacuum drying temperature is 60-120 ℃, and the drying time is 6-12 hours;
in the step (4), the volume ratio of the hydrogen-argon mixed gas is preferably 20-50%, the treatment temperature is preferably 600-900 ℃, and the temperature rise rate of the programmed temperature rise is preferably 2-10 ℃/min; the time for introducing the carbon source is preferably 5-30 minutes; the flow rate of the introduced carbon source is preferably 60-200 mL/min;
in the step (6), the preferable drying temperature is 60-120 ℃, and the drying time is 6-12 hours;
the products of examples 1-12 of the invention were tested by the following instruments and methods:
the morphology of the products of examples 1-12 was characterized by Transmission Electron Microscopy (TEM);
the structural information of examples 3-6 was analyzed by X-ray diffraction spectroscopy (XRD);
the hydrogen production performance by decomposing hydrogen sulfide of examples 1 to 6 was measured in an electrocatalytic hydrogen sulfide system.
Examples 1-3 are for modulating the metal or alloy species; examples 3-6 were prepared by adjusting the calcination temperature; examples 6-8 were prepared by adjusting the size of silica spheres; examples 9-12 are the modulation of the time for feeding the carbon source.
Example 1
1. 1.8g of urea and 3.6mmol of cobalt nitrate are dissolved in 100mL of deionized water under stirring until the solution is clear and transparent, 1.8g of silica spheres with the diameter of about 70nm are added, and the mixture is uniformly dispersed by ultrasonic.
2. Placing the dispersed solution of (1) in a round-bottom flask, carrying out reflux treatment at 100 ℃ for 12 hours under stirring, standing, cooling to room temperature, washing with water, centrifuging to obtain a precipitate, and drying in vacuum at 60 ℃ for 12 hours.
3. Placing the dried sample in the step (2) in a tube furnace in Ar: H2The temperature was raised to 600 ℃ with a 5 ℃/min program under a 3:1 atmosphere, and acetonitrile was bubbled with Ar at a flow rate of 60mL/min at this temperature for 15 min.
4. And (4) mechanically stirring the sample obtained in the step (3) in a 10% hydrofluoric acid aqueous solution, treating for 6 hours at normal temperature, washing with water and ethanol respectively, and performing suction filtration until the solution is neutral.
5. And (5) drying the sample obtained in the step (4) at the temperature of 80 ℃ for 12h to obtain the carbon-encapsulated metal cobalt nanoparticles.
The transmission electron microscope of the material shows that the carbon-encapsulated cobalt nanoparticles are dispersed on the in-situ generated carbon nano-tubes; the high-resolution transmission electron microscope shows that the carbon layer is a single layer, and the particle size of the metal nano-particles is 4-6 nm; and the sample is magnetic.
Example 2
1. 1.8g of urea and 3.6mmol of nickel acetate are dissolved in 100mL of deionized water under stirring until the solution is clear and transparent, 1.8g of silica spheres with the diameter of about 70nm are added, and the mixture is uniformly dispersed by ultrasonic.
2. Placing the dispersed solution of (1) in a round-bottom flask, carrying out reflux treatment at 100 ℃ for 12 hours under stirring, standing, cooling to room temperature, washing with water, centrifuging to obtain a precipitate, and drying in vacuum at 60 ℃ for 12 hours.
3. Placing the dried sample in the step (2) in a tube furnace in Ar: H2The temperature was raised to 600 ℃ with a 5 ℃/min program under a 3:1 atmosphere, and acetonitrile was bubbled with Ar at a flow rate of 60mL/min at this temperature for 15 min.
4. And (4) mechanically stirring the sample obtained in the step (3) in a 10% hydrofluoric acid aqueous solution, treating for 6 hours at normal temperature, washing with water and ethanol respectively, and performing suction filtration until the solution is neutral.
5. And (5) drying the sample obtained in the step (4) at the temperature of 80 ℃ for 12h to obtain the carbon-encapsulated metal cobalt nanoparticles.
The transmission electron microscope of the material shows that the carbon-encapsulated nickel nanoparticles are dispersed on the in-situ generated carbon nanotubes (see fig. 1 a); the carbon layer is a single layer, and the particle size of the metal nano-particles is 4-6nm (shown in figure 1b) as shown by a high-resolution transmission electron microscope; and the sample is magnetic.
Example 3
1. 1.8g of urea, 1.80mmol of cobalt nitrate and 1.80mmol of nickel acetate are dissolved in 100mL of deionized water with stirring until the solution is clear and transparent, 1.8g of silica spheres with a diameter of about 70nm are added, and the mixture is dispersed uniformly by ultrasonic.
2. Placing the dispersed solution of (1) in a round-bottom flask, carrying out reflux treatment at 100 ℃ for 12 hours under stirring, standing, cooling to room temperature, washing with water, centrifuging to obtain a precipitate, and drying in vacuum at 60 ℃ for 12 hours.
3. Placing the dried sample in the step (2) in a tube furnace in Ar: H2The temperature was raised to 600 ℃ with a 5 ℃/min program under a 3:1 atmosphere, and acetonitrile was bubbled with Ar at a flow rate of 60mL/min at this temperature for 15 min.
4. And (4) mechanically stirring the sample obtained in the step (3) in a 10% hydrofluoric acid aqueous solution, treating for 6 hours at normal temperature, washing with water and ethanol respectively, and performing suction filtration until the solution is neutral.
5. And (5) drying the sample obtained in the step (4) at the temperature of 80 ℃ for 12h to obtain the carbon-encapsulated metal cobalt nanoparticles.
The transmission electron microscope of the material shows that the carbon-encapsulated cobalt-nickel alloy nanoparticles are dispersed on the in-situ generated carbon nanotubes (see fig. 2 a); the carbon layer is a single layer, and the particle size of the metal nano-particles is 4-6nm (shown in figure 2b) as shown by a high-resolution transmission electron microscope; a diffraction peak of the cobalt-nickel alloy appears in an X-ray diffraction spectrum (see figure 7), and the packaged nano particles are cobalt-nickel in an alloy state; the C (002) peak is obvious, which indicates that the material contains a large amount of carbon nanotubes; and the sample is magnetic.
Discussion of the results: in examples 1 to 3, under the premise of other consistent conditions (the baking temperature is 600 ℃, acetonitrile is introduced for 15min), the single-layer carbon-encapsulated metal particle material dispersed on the in-situ generated carbon nanotube can be prepared by modulating the metal species.
Example 4
1. 1.8g of urea, 1.80mmol of cobalt nitrate and 1.80mmol of nickel acetate are dissolved in 100mL of deionized water with stirring until the solution is clear and transparent, 1.8g of silica spheres with a diameter of about 70nm are added, and the mixture is dispersed uniformly by ultrasonic.
2. Placing the dispersed solution of (1) in a round-bottom flask, carrying out reflux treatment at 100 ℃ for 12 hours under stirring, standing, cooling to room temperature, washing with water, centrifuging to obtain a precipitate, and drying in vacuum at 60 ℃ for 12 hours.
3. Placing the dried sample in the step (2) in a tube furnace in Ar: H2The temperature is raised to 700 ℃ by a program of 5 ℃/min under the atmosphere of 3:1, and acetonitrile is bubbled by Ar with the flow rate of 60mL/min under the temperature for 15 min.
4. And (4) mechanically stirring the sample obtained in the step (3) in a 10% hydrofluoric acid aqueous solution, treating for 6 hours at normal temperature, washing with water and ethanol respectively, and performing suction filtration until the solution is neutral.
5. And (5) drying the sample obtained in the step (4) at the temperature of 80 ℃ for 12h to obtain the carbon-encapsulated metal cobalt nanoparticles.
The transmission electron microscope of the material shows that the carbon-encapsulated cobalt-nickel alloy nanoparticles are dispersed on the in-situ generated carbon nanotubes (see fig. 3 a); the carbon layer is a single layer as shown by a high-resolution transmission electron microscope, and the particle size of the metal nano-particles is 4-6nm (shown in figure 3 b); a diffraction peak of the cobalt-nickel alloy appears in an X-ray diffraction spectrum (see figure 7), and the packaged nano particles are cobalt-nickel in an alloy state; and the sample is magnetic.
Example 5
1. 1.8g of urea, 1.80mmol of cobalt nitrate and 1.80mmol of nickel acetate are dissolved in 100mL of deionized water with stirring until the solution is clear and transparent, 1.8g of silica spheres with a diameter of about 70nm are added, and the mixture is dispersed uniformly by ultrasonic.
2. Placing the dispersed solution of (1) in a round-bottom flask, carrying out reflux treatment at 100 ℃ for 12 hours under stirring, standing, cooling to room temperature, washing with water, centrifuging to obtain a precipitate, and drying in vacuum at 60 ℃ for 12 hours.
3. Placing the dried sample in the step (2) in a tube furnace in Ar: H2The temperature is raised to 800 ℃ by a program of 5 ℃/min under the atmosphere of 3:1, and acetonitrile is bubbled by Ar with the flow rate of 60mL/min under the temperature for 15 min.
4. And (4) mechanically stirring the sample obtained in the step (3) in a 10% hydrofluoric acid aqueous solution, treating for 6 hours at normal temperature, washing with water and ethanol respectively, and performing suction filtration until the solution is neutral.
5. And (5) drying the sample obtained in the step (4) at the temperature of 80 ℃ for 12h to obtain the carbon-encapsulated metal cobalt nanoparticles.
In the preparation process of the material, firstly, the cobalt-nickel layered hydroxide (CoNi-LDH) is coated on SiO2The surface of the sphere (70nm) was examined by transmission electron microscopy as shown in FIG. 4 a. Then introducing a carbon source at high temperature to obtain carbon-encapsulated cobalt-nickel metal nanoparticles growing on SiO2A sample of spheres (70nm) was obtained by transmission electron microscopy as shown in FIG. 4 b. The transmission electron microscope of the material finally obtained after acid etching shows that the carbon-encapsulated cobalt-nickel alloy nanoparticles are gathered together and almost have no carbon nanotube; the high resolution transmission electron microscope (see fig. 4c) shows that the carbon layer is a single layer, and the particle size of the metal nano-particles is 4-6 nm; a diffraction peak of the cobalt-nickel alloy appears in an X-ray diffraction spectrum (see figure 7), and the packaged nano particles are cobalt-nickel in an alloy state; and the sample is magnetic.
Example 6
1. 1.8g of urea, 1.80mmol of cobalt nitrate and 1.80mmol of nickel acetate are dissolved in 100mL of deionized water with stirring until the solution is clear and transparent, 1.8g of silica spheres with a diameter of about 70nm are added, and the mixture is dispersed uniformly by ultrasonic.
2. Placing the dispersed solution of (1) in a round-bottom flask, carrying out reflux treatment at 100 ℃ for 12 hours under stirring, standing, cooling to room temperature, washing with water, centrifuging to obtain a precipitate, and drying in vacuum at 60 ℃ for 12 hours.
3. Placing the dried sample in the step (2) in a tube furnace in Ar: H2The temperature is raised to 900 ℃ by a program of 5 ℃/min under the atmosphere of 3:1, and acetonitrile is bubbled by Ar with the flow rate of 60mL/min under the temperature for 15 min.
4. And (4) mechanically stirring the sample obtained in the step (3) in a 10% hydrofluoric acid aqueous solution, treating for 6 hours at normal temperature, washing with water and ethanol respectively, and performing suction filtration until the solution is neutral.
5. And (5) drying the sample obtained in the step (4) at the temperature of 80 ℃ for 12h to obtain the carbon-encapsulated metal cobalt nanoparticles.
The transmission electron microscope of the material shows that the carbon-encapsulated cobalt-nickel alloy nanoparticles are gathered together and almost have no carbon nano tube; the high-resolution transmission electron microscope shows that the carbon layer is a single layer, and the particle size of the metal nano-particles is 4-6 nm; a diffraction peak of the cobalt-nickel alloy appears in an X-ray diffraction spectrum (see figure 7), and the packaged nano particles are cobalt-nickel in an alloy state; and the sample is magnetic.
Discussion of the results: in examples 3 to 6, under the premise of other consistent conditions (acetonitrile is introduced for 15min), the preparation of single-layer carbon-encapsulated cobalt-nickel metal can be realized by changing the baking temperature, and the generation amount of carbon nanotubes can be changed. When the roasting temperature is 600 ℃, a large amount of carbon nanotubes are generated; the generation amount of the carbon nano tube is reduced after the carbon nano tube is roasted at 700 ℃; when the roasting temperature reaches 800 ℃ and above, the carbon nano tube is not generated basically.
Example 7
1. 1.8g of urea, 1.80mmol of cobalt nitrate and 1.80mmol of nickel acetate are dissolved in 100mL of deionized water with stirring until the solution is clear and transparent, 1.8g of silica spheres with the diameter of about 150nm are added, and the mixture is dispersed uniformly by ultrasonic.
2. Placing the dispersed solution of (1) in a round-bottom flask, carrying out reflux treatment at 100 ℃ for 12 hours under stirring, standing, cooling to room temperature, washing with water, centrifuging to obtain a precipitate, and drying in vacuum at 60 ℃ for 12 hours.
3. Placing the dried sample in the step (2) in a tube furnace in Ar: H2Is 3:1 atmosphere, the temperature is programmed to 900 ℃ at 5 ℃/min, and acetonitrile is bubbled with Ar at the flow rate of 60mL/min at the temperature for 15 min.
4. And (4) mechanically stirring the sample obtained in the step (3) in a 10% hydrofluoric acid aqueous solution, treating for 6 hours at normal temperature, washing with water and ethanol respectively, and performing suction filtration until the solution is neutral.
5. And (5) drying the sample obtained in the step (4) at the temperature of 80 ℃ for 12h to obtain the carbon-encapsulated metal cobalt nanoparticles.
The transmission electron microscope of the material shows that the carbon-encapsulated cobalt-nickel alloy nanoparticles are gathered together and almost have no carbon nano tube; the high-resolution transmission electron microscope shows that the carbon layer is a single layer, and the particle size of the metal nano-particles is 4-6 nm.
Example 8
1. 1.8g of urea, 1.80mmol of cobalt nitrate and 1.80mmol of nickel acetate are dissolved in 100mL of deionized water with stirring until the solution is clear and transparent, 1.8g of silica spheres with the diameter of about 400nm are added, and the mixture is dispersed uniformly by ultrasonic.
2. Placing the dispersed solution of (1) in a round-bottom flask, carrying out reflux treatment at 100 ℃ for 12 hours under stirring, standing, cooling to room temperature, washing with water, centrifuging to obtain a precipitate, and drying in vacuum at 60 ℃ for 12 hours.
3. Placing the dried sample in the step (2) in a tube furnace in Ar: H2The temperature is raised to 900 ℃ by a program of 5 ℃/min under the atmosphere of 3:1, and acetonitrile is bubbled by Ar with the flow rate of 60mL/min under the temperature for 15 min.
4. And (4) mechanically stirring the sample obtained in the step (3) in a 10% hydrofluoric acid aqueous solution, treating for 6 hours at normal temperature, washing with water and ethanol respectively, and performing suction filtration until the solution is neutral.
5. And (5) drying the sample obtained in the step (4) at the temperature of 80 ℃ for 12h to obtain the carbon-encapsulated metal cobalt nanoparticles.
After introducing carbon source at high temperature, transmission electron microscopy (see FIG. 5a) of the sample shows that carbon-encapsulated cobalt-nickel metal nanoparticles are densely distributed in SiO2No carbon nanotubes were formed on the surface of the spheres (400 nm). The transmission electron microscope of the material after acid etching shows that the carbon-packaged cobalt-nickel alloy nanoparticles are gathered together and almost have no carbon nanotube; high resolution transmission electron microscopy (see FIG. 5b) indicates that the carbon layer is a single layer, metal nano-scaleThe particle size of the particles is 4-6 nm.
Discussion of the results: under the premise of consistent other conditions (acetonitrile is introduced at 900 ℃ and kept for 15min), the nitrogen-doped single-layer carbon-encapsulated cobalt-nickel alloy material can be prepared by changing the size of the silicon dioxide spheres, and basically no carbon nano tube is generated.
Example 9
1. 1.8g of urea, 1.80mmol of cobalt nitrate and 1.80mmol of nickel acetate are dissolved in 100mL of deionized water with stirring until the solution is clear and transparent, 1.8g of silica spheres with the diameter of about 400nm are added, and the mixture is dispersed uniformly by ultrasonic.
2. Placing the dispersed solution of (1) in a round-bottom flask, carrying out reflux treatment at 100 ℃ for 12 hours under stirring, standing, cooling to room temperature, washing with water, centrifuging to obtain a precipitate, and drying in vacuum at 60 ℃ for 12 hours.
3. Placing the dried sample in the step (2) in a tube furnace in Ar: H2Heating to 900 ℃ with a program of 5 ℃/min under the atmosphere of 3:1, introducing 100mL/min methane at the temperature, and maintaining for 5 min.
4. And (4) mechanically stirring the sample obtained in the step (3) in a 10% hydrofluoric acid aqueous solution, treating for 6 hours at normal temperature, washing with water and ethanol respectively, and performing suction filtration until the solution is neutral.
5. And (5) drying the sample obtained in the step (4) at the temperature of 80 ℃ for 12h to obtain the carbon-encapsulated metal cobalt nanoparticles.
After introducing carbon source at high temperature, high resolution transmission electron microscope (see fig. 6a) of the sample shows that carbon-encapsulated cobalt-nickel metal nanoparticles grow on SiO2No carbon nano tube is generated on the surface of the ball (400nm), the carbon layer is a single layer, and the particle size of the metal nano particle is 4-6 nm.
Example 10
1. 1.8g of urea, 1.80mmol of cobalt nitrate and 1.80mmol of nickel acetate are dissolved in 100mL of deionized water with stirring until the solution is clear and transparent, 1.8g of silica spheres with the diameter of about 400nm are added, and the mixture is dispersed uniformly by ultrasonic.
2. Placing the dispersed solution of (1) in a round-bottom flask, carrying out reflux treatment at 100 ℃ for 12 hours under stirring, standing, cooling to room temperature, washing with water, centrifuging to obtain a precipitate, and drying in vacuum at 60 ℃ for 12 hours.
3. Placing the dried sample in the step (2) in a tube furnace in Ar: H2Heating to 900 ℃ with a program of 5 ℃/min under the atmosphere of 3:1, introducing 100mL/min methane at the temperature, and maintaining for 10 min.
4. And (4) mechanically stirring the sample obtained in the step (3) in a 10% hydrofluoric acid aqueous solution, treating for 6 hours at normal temperature, washing with water and ethanol respectively, and performing suction filtration until the solution is neutral.
5. And (5) drying the sample obtained in the step (4) at the temperature of 80 ℃ for 12h to obtain the carbon-encapsulated metal cobalt nanoparticles.
After introducing carbon source at high temperature, high resolution transmission electron microscope (see fig. 6b) of the sample shows that carbon-encapsulated cobalt-nickel metal nanoparticles grow on SiO2No carbon nano tube is generated on the surface of the ball (400nm), the carbon layer is two layers, and the particle size of the metal nano particle is 4-6 nm.
Example 11
1. 1.8g of urea, 1.80mmol of cobalt nitrate and 1.80mmol of nickel acetate are dissolved in 100mL of deionized water with stirring until the solution is clear and transparent, 1.8g of silica spheres with the diameter of about 400nm are added, and the mixture is dispersed uniformly by ultrasonic.
2. Placing the dispersed solution of (1) in a round-bottom flask, carrying out reflux treatment at 100 ℃ for 12 hours under stirring, standing, cooling to room temperature, washing with water, centrifuging to obtain a precipitate, and drying in vacuum at 60 ℃ for 12 hours.
3. Placing the dried sample in the step (2) in a tube furnace in Ar: H2Heating to 900 ℃ with a program of 5 ℃/min under the atmosphere of 3:1, introducing 100mL/min methane at the temperature, and maintaining for 20 min.
4. And (4) mechanically stirring the sample obtained in the step (3) in a 10% hydrofluoric acid aqueous solution, treating for 6 hours at normal temperature, washing with water and ethanol respectively, and performing suction filtration until the solution is neutral.
5. And (5) drying the sample obtained in the step (4) at the temperature of 80 ℃ for 12h to obtain the carbon-encapsulated metal cobalt nanoparticles.
After introducing carbon source at high temperature, high resolution transmission electron microscope (see fig. 6c) of the sample shows that carbon-encapsulated cobalt-nickel metal nanoparticles grow on SiO2No carbon nanotube is formed on the surface of the sphere (400nm), the carbon layer is two layers, and the metal nanoparticles are arranged on the surfaceThe particle diameter of the particles is 4-6nm, and SiO2The surface of the ball is coated by carbon deposit.
Example 12
1. 1.8g of urea, 1.80mmol of cobalt nitrate and 1.80mmol of nickel acetate are dissolved in 100mL of deionized water with stirring until the solution is clear and transparent, 1.8g of silica spheres with the diameter of about 400nm are added, and the mixture is dispersed uniformly by ultrasonic.
2. Placing the dispersed solution of (1) in a round-bottom flask, carrying out reflux treatment at 100 ℃ for 12 hours under stirring, standing, cooling to room temperature, washing with water, centrifuging to obtain a precipitate, and drying in vacuum at 60 ℃ for 12 hours.
3. Placing the dried sample in the step (2) in a tube furnace in Ar: H2Heating to 900 ℃ with a program of 5 ℃/min under the atmosphere of 3:1, introducing 100mL/min methane at the temperature, and maintaining for 30 min.
4. And (4) mechanically stirring the sample obtained in the step (3) in a 10% hydrofluoric acid aqueous solution, treating for 6 hours at normal temperature, washing with water and ethanol respectively, and performing suction filtration until the solution is neutral.
5. And (5) drying the sample obtained in the step (4) at the temperature of 80 ℃ for 12h to obtain the carbon-encapsulated metal cobalt nanoparticles.
After carbon source is introduced at high temperature, the high-resolution transmission electron microscope of the sample shows that the carbon-encapsulated cobalt-nickel metal nanoparticles grow on SiO2No carbon nanotube is formed on the surface of the sphere (400nm), the carbon layer is two layers, the particle diameter of the metal nano-particles is 4-6nm, and SiO is2Carbon deposit coating exists on the surface of the ball; the transmission electron microscope (see fig. 6d) of the material obtained after acid etching shows that a carbon cage structure of about 400nm is formed, and carbon-packaged cobalt-nickel metal nanoparticles are densely distributed in the material; the sample was magnetic.
Discussion of the results: examples 9-12 the number of carbon layers deposited on the metal surface was controlled by adjusting the time for feeding methane under otherwise identical conditions. The carbon deposition process firstly occurs on the metal surface to form a single-layer carbon packaging metal structure; along with the increase of the methane introducing time, the carbon layer on the metal surface is increased to two layers; the time is further increased, carbon deposition also begins on the surface of the silica spheres, and finally the carbon coats the surface of the silica spheres.
Application example 1
The carbon-encapsulated metal nanoparticles obtained in examples 1 to 3 were used as a catalyst material for oxidation reaction of hydrogen sulfide hydrogen production system by electrocatalytic decomposition, and the influence of cobalt, nickel and cobalt-nickel alloys having the same metal content as different metal centers on the catalytic performance was examined.
1. Building a test system: the testing device is a three-electrode system, the reference electrode is Hg/HgO (1M NaOH solution), the counter electrode is a C rod, the working electrode is a glassy carbon electrode with the diameter of 5mm, and the electrolyte is 1M NaOH and 1M Na2And (5) preparing an S solution. And in the test process, a gas bubbling device is adopted to carry out Ar saturation on the electrolyte. The working electrode was subjected to a series of cleaning processes including Al prior to testing2O3Polishing, washing with absolute ethyl alcohol and deionized water, and the like. Preparation of a working electrode: adding 5mg of catalyst sample into 2mL of absolute ethyl alcohol, performing ultrasonic dispersion for 5min, adding 50 mu L of 5% Nafion/isopropanol solution, performing ultrasonic dispersion for 20min to obtain catalyst slurry, dropwise adding 25 mu L of the slurry onto a glassy carbon electrode, and naturally drying to be tested, wherein the loading capacity of the catalyst is 0.32mg/cm2。
2. The catalytic performance evaluation method comprises the following steps: the temperature of the electrolytic cell is maintained at 25 ℃, and the oxidation S of the catalyst is tested through a polarization curve2-The capacity of (c) is compared with the potential required for the catalyst when a certain oxidation current density is reached.
3. Compared with the material of carbon-encapsulated single-metal cobalt or nickel nanoparticles, the carbon-encapsulated cobalt-nickel alloy nanoparticles have lower overpotential, and the oxidation current density of the carbon-encapsulated cobalt-nickel alloy nanoparticles reaches 61mA/cm at the same potential of 0.45V vs2And the carbon-encapsulated cobalt nanoparticles were 27mA/cm2The carbon-encapsulated nickel nanoparticles are 50mA/cm2(see FIG. 8). Therefore, the catalytic activity of the catalyst in the hydrogen production reaction of hydrogen sulfide through electrocatalytic oxidation can be effectively improved by properly adjusting the types and alloys of the carbon-encapsulated metal nanoparticles.
Application example 2
The carbon-encapsulated metal nanoparticles obtained in examples 3 to 6 were used as a catalyst material for the oxidation reaction of a hydrogen production system by electrocatalytic decomposition of hydrogen sulfide, and the influence of different calcination temperatures on the catalytic performance of the carbon-encapsulated metal nanoparticle catalyst material was examined.
1. Building a test system: the testing device is a three-electrode system, the reference electrode is Hg/HgO (1M NaOH solution), the counter electrode is a C rod, the working electrode is a glassy carbon electrode with the diameter of 5mm, and the electrolyte is 1M NaOH and 1M Na2And (5) preparing an S solution. And in the test process, a gas bubbling device is adopted to carry out Ar saturation on the electrolyte. The working electrode was subjected to a series of cleaning processes including Al prior to testing2O3Polishing, washing with absolute ethyl alcohol and deionized water, and the like. Preparation of a working electrode: adding 5mg of catalyst sample into 2mL of absolute ethyl alcohol, performing ultrasonic dispersion for 5min, adding 50 mu L of 5% Nafion/isopropanol solution, performing ultrasonic dispersion for 20min to obtain catalyst slurry, dropwise adding 25 mu L of the slurry onto a glassy carbon electrode, and naturally drying to be tested, wherein the loading capacity of the catalyst is 0.32mg/cm2。
2. The catalytic performance evaluation method comprises the following steps: the temperature of the electrolytic cell is maintained at 25 ℃, and the oxidation S of the catalyst is tested through a polarization curve2-The capacity of (c) is compared with the potential required for the catalyst when a certain oxidation current density is reached.
3. Compared with the material prepared by roasting at higher temperature, the carbon-encapsulated cobalt-nickel alloy nano material prepared by roasting at 600 ℃ has lower overpotential, 0.5V vs. RHE under the same potential, and the oxidation current density of the material obtained by roasting at 600 ℃ reaches 87mA/cm2The oxidation current densities of materials prepared by roasting at 700,800 and 900 ℃ are 71,6 and 10mA/cm respectively along with the rise of the roasting temperature2(see FIG. 9). The TEM characterization of the combined material shows that the material prepared by roasting at 800 ℃ basically has no generation of carbon nanotubes, so that the in-situ generated carbon nanotubes are presumed to have great influence on the conductivity of the catalyst, and the existence of the carbon nanotubes can effectively improve the conductivity of the material so as to improve the catalytic performance of the material. Therefore, the roasting preparation temperature of the carbon-encapsulated metal nanoparticles is properly adjusted, the morphology of the material can be effectively changed, and the catalytic activity of the catalyst in the hydrogen production reaction of the electrocatalytic oxidation of hydrogen sulfide is further influenced.
Claims (10)
1. A preparation method of a carbon-encapsulated metal nanoparticle material is characterized by comprising the following steps:
(1) converting metal cation salt and alkaline precursor into layered metal hydroxide by a coprecipitation method, and depositing the layered metal hydroxide on the surface of the silicon dioxide nanospheres;
(2) roasting in a reducing atmosphere to reduce the metal hydroxide into metal, introducing a carbon source, and depositing a carbon layer on the surface of the metal by using a chemical vapor deposition method;
(3) acid etching to remove the silicon dioxide to obtain the carbon-encapsulated metal nano-particle material;
the metal cation in the metal cation salt is at least one of magnesium, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc or ruthenium; the metal cation salt is at least one of nitrate, sulfate, chloride or acetate of the metal cation;
the alkaline precursor is at least one of urea, hexamethylene tetramine, ammonium fluoride, sodium hydroxide, sodium carbonate or ammonia water.
2. The production method according to claim 1,
the method realizes the regulation of the carbon layer deposited on the metal surface by regulating the time for introducing the carbon source.
3. The production method according to claim 1,
the mass ratio of the metal cation salt to the silicon dioxide nanospheres in the step (1) is 0.1-5: 1; the molar ratio of any two of the more than two metal cation salts is 1: 20-20: 1;
the diameter of the silicon dioxide ball in the step (1) is 20-400 nm;
in the step (1), the coprecipitation temperature is 80-140 ℃ and the treatment is carried out for 6-24 hours.
4. The preparation method according to claim 1, wherein the inert atmosphere and hydrogen gas in the reducing atmosphere in the step (2) have a composition ratio of 1-5: 1; the inert gas is one of nitrogen, argon or helium; the temperature programming end point temperature of the roasting is 500-1000 ℃, and the temperature raising rate of the temperature programming is 0.5-20 ℃/min.
5. The method according to claim 1, wherein the carbon source in the step (2) is at least one of methanol, ethanol, pyridine, pyrrole, acetonitrile, methane, ethane, ethylene, acetylene, or propylene; the flow rate of the introduced carbon source is 10-500 mL/min, and the maintaining time is 5-60 minutes.
6. The method according to claim 1, wherein the acid etching in step (3) is performed with a hydrofluoric acid solution having a concentration of 5-20% for 4-8 hours.
7. The carbon-encapsulated metal nanoparticle material prepared by the method of any one of claims 1 to 6, wherein the metal nanoparticles are independently encapsulated in the carbon layer in a metal state or an alloy state, and the particle size of the metal nanoparticles is 4 to 8 nm.
8. The carbon-encapsulated metal nanoparticle material of claim 7, said carbon-encapsulated metal nanoparticle material metal nanoparticles being dispersed on in-situ generated carbon nanotubes.
9. The carbon-encapsulated metal nanoparticle material of claim 7, the carbon layer being 1, 2, or 3 layers.
10. The carbon-encapsulated metal nanoparticle material of claim 7, 8 or 9 as an electrode material for application in hydrogen production systems by electrocatalytic decomposition of hydrogen sulfide.
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Application publication date: 20200207 Assignee: Guoke green hydrogen (Huzhou) Technology Co.,Ltd. Assignor: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Contract record no.: X2022990000892 Denomination of invention: A Preparation Method of Carbon Encapsulated Metal Nanoparticles with Controllable Number of Layers Granted publication date: 20210402 License type: Common License Record date: 20221103 |
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